Red anthraquinone dyes containing ester groups

ABSTRACT

Red 1-amino-4-hydroxyanthraquinone dyes which contain in the 2position, attached by way of an oxygen atom, a hydrocarbon radical which in turn bears an esterified hydroxyl group. The dyes are particularly suitable for dyeing polyester textile material.

United States Patent Maier Aug. 29, 1972 54 RED ANTHRAQUINONE DYESReferences Cited CONTAINING ESTER GROUPS UNITED STATES PATENTS [72]Inventor: Karl Maler, Ludwlgshafen, Germany 3,445,485 5/1969 Straley..260/380 3,530,150 9/ I970 Rickenbacher ..260/380 [73] Assignee:Badische Anilin- & Soda Fabrlk Aktiengesellschalt Land Rhineland- OTHERPUBLICATIONS Pfalz, Germany Akarnatsu et al., as cited in Chem.Abstracts, 60, 22 Filed: Sept. 5, 1969 14646- [21] Appl- N -I ,7 PrimaryExaminer-Lorraine A. Weinberger Assistant Examiner-E. Jane SkellyAttorney-Johnston, Root, OKeeffe, Keil, Thompson [30] ForeignApplication Pnonty Data & Sh n1 Sept. 22, 1968 Germany ..P 17 94 115.0

[57] ABSTRACT [52] US. Cl. ..260/376, 8/39, 8/40 Red l amino 4hydmxyamhraquinone dyes which Int. Cl. ..C09b contain in the 2 p itionattached way of an OK. ygen atom, a hydrocarbon radical which in turnbears Field of Search ..260/376, 380

an esterified hydroxyl group. The dyes are particularly suitable fordyeing polyester textile material.

3 Claims, No Drawings RED ANTHRAQUINONE DYESCONTAINING ESTER GROUPS Thisinvention relates to new, valuable red anthraquinone dyes containingester groups, their production and the use of these dyes for dyeing and5 printing semisynthetic and synthetic textile material.

The dyes according to the invention have the'formula:

n ()H (I) in which X denotes an aliphatic or cycloaliphatic hydrocarbonradical having from two to nine carbon atoms which may also contain thebridging member O-- and R denotes a hydrogen atom, an aliphatichydrocarbon radical having one to five carbon atoms which may bearhalogen atoms, cyano groups, keto groups, carboxylic ester groups orphenyl groups as substituents, or a phenyl radical which may bearhalogen atoms, hydroxyl groups, methyl groups, methoxy groups, nitrogroups, amino groups or carboxylic ester groups as substituents. Linearor branched saturated radicals are suitable as aliphatic radicals Xhaving two to nine carbon atoms which may contain the bridging member-O-. The following radicals are given by way of example:

. m which n denotes one of the integers 2 to 9, m denotes l, 2 or 3, zdenotes zero or 1 and z denotes zero, 1, 2 or 3. An example of acycloaliphatic radical of the specified type is the radical Linear orbranched, saturated and unsaturated radical having one to five carbonatoms, which may contain the said substituents, are suitable as thealiphatic hydrocarbon radicals R.

The following are given as examples of the radical R:

3 CzHsOOC NHz with an acid having the formula R-COOl-l or a functionalderivative of such an acid by a conventional method. For example theprocedure may consist in treating the anthraquinone derivative havingthe formula (II) with the appropriate acid anhydride in the presence ofa base such as pyridine at temperatures up to 40 C or with the free acidat temperatures above C, advantageously at the boiling temperature ofthe acid, and in the presence or absence of an esterification catalystsuch as sodium acetate or p-toluenesulfonic acid. The said acids or acidderivatives are used in at least the stoichiometric amount withreference to the weight of the compound (II), but advantageously with anexcess of for example twice to three times.

Dyes having the formula (I) which contain a carboxylic ester group inthe radical R are advantageously prepared by reaction of the startingmaterial having the formula (II) with the appropriate diearboxylicester. Only-one of the two ester groups reacts, the new dye beingformed.

Examples of acids having the formula R--COOH are: formic acid, aceticacid, propionic acid, chloroacetic acid, bromoacetic acid,dichloroacetic acid, chloropropionic acid, cyanoacetic acid, acrylicacid, phenylacetic acid, acetoacetic acid, butyric acid, isobutyricacid, valeric acid, isovaleric acid, malonic acid, fumaric acid, pivalicacid, methoxyacetic acid, benzoic acid, salicylic acid, succinic acid,hexahydrobenzoic acid, phthalic acid and terephthalic acid.

Some of the anthraquinone derivatives having'the formula (II) which areused as starting materials for the production of the new dyes are knownfrom U.K. Pat. Specification No. 982,267. Since these starting materialsare themselves dyes having good fastness properties it is surprisingthat the dyes obtained from these known dyes by esterification have amuch better affinity for polyester fibers, so that the dye yield isincreased. It is also surprising that the excellent fastness propertiesof the starting dyes having the formula (II) are not impaired byesterification to form the dyes according to this invention and thatfastness to heat setting is even improved.

The dyes according to this invention are valuable dyes which in thedyeing of semisynthetic and synthetic textile material such as textilematerial of cellulose acetate, triacetate, polyamide, but particularlypolyester fibrous material, are distinguished by excellent fastnessproperties and by outstanding affinity. It is also possible to usemixtures of the dyes for dyeing or printing.

The invention is illustrated by the following Examples, in which partsand percentages are by weight.

EXAMPLE 1 25 parts of1-amino-4-hydroxy-2-(w-hydroxyhexoxy)-anthraquinone is boiled with 70parts of glacial acetic acid and 1 part of anhydrous sodium acetate foreight hours under reflux. The mixture is diluted with 70 parts ofmethanol and cooled, followed by suction filtration. 27 parts of the reddye l-amino-4-hydroxy-2- (w-acetoxyhexoxy)-anthraquinone is obtainedhaving a melting point of 130 to 13 15 C (from butanol).

EXAMPLE 2 parts of 1-amino-4-hydroxy-2-(m-hydroxyhexoxy)-anthraquinoneis heated for 6 hours at 90 C with 100 parts of butyl formate and 6parts of p-toluenesulfonic acid. The whole is cooled, suction filteredand washed with methanol. 19 parts of the red dye l-amino-4-hydroxy-2-(m-formoyloxyhexoxy)-anthraquin0ne is obtained having amelting point of 150 to 151 C (from butanol).

EXAMPLE 3 20 parts of1-amino-4-hydroxy-2-(w-hydroxyhexoxy)-anthraquinone is heated for 6hours at 120 C with 50 parts of propionic acid and 0.2 part oftoluene-sulfonic acid and diluted with 50 parts of methanol. Thereaction mixture is cooled, suction filtered and washed with methanoland water. 21.9 parts of the dye 1-amino-4-hydroxy-2-(w-propionyloxyhexoxy)- anthraquinone having a meltingpoint of 129 to 130 C is obtained.

By following the procedure described in the foregoing Examples but usinganthraquinone derivatives having the formula (11) and having theradicals X indicated in the following Table and the specified acids oracid derivatives, red dyes containing ester groups and having theradicals R indicated in the Table are obtained.

The following abbreviations are used in the Table:

Ex number of the Example Acid acid or acid derivatives M. Pt. meltingpoint in "C after recrystallization from the solvent indicated inparenthesis CB chlorobenzene acid dichloro- -CHC1, acetic acid ethyl-Cl-l acetate acetic -C1 1 acid dichloro- -Cl-1C1, acetic acid acetic-CH acid acetic -C1-l acid acetic -C1*l anhydride ethyl -CH,CHpropionate monochloroCH Cl acetic acid dichloro- -C1-1C1 acetic acidethyl mono-CH Br bromoacetate ethyl -CH -CN cyanoacetate B-chloro- -C1-1-C1-1 Cl propiomc ad a, a-dichlor G(Cl) -CH propiomc acid phenylaceticacid crotonic -CH=CH-CH;, acid acetic -CH acid acetic -CH;, acid acetic-CH acid acetic -CH acid acetic -Cl-1;, acid ethyl aceto-Cl-l -CO-Cl-lacetate benzoic methyl p-hydroxybenzoate 151-152 (B) 1110-131 (13)124-125 (B) 146-147 (B) 33 {CHM- methyl H 142-143 salicylate (B) diethyl-Cl-1,Cl-l COOC,,l'l 1091 succinate (E) iso- -CH C(CH,)H-CH;, 127-128valeric (B) acid o-chloro- 1 38-1 39 benzoic Q (E/Be) acid butyric -Cl'1 1 18.5-1 1 9 acid 0) phenyl- 122-123 acetic (B) acid methyl I 139-140 mum CH C=CH2 (B) crylate hexahydro- 143-144 benzoic H acid t.,

dimethyl -CH cH-coocH 123.5-12

4 fumarate (B) diethyl -CH COOCH 97-98 malonate (B) o-methoxy- 136-137benzoic --Q acid O 0 Ha diethyl 69-70 phthalate (B) C O O C 2H5 pivalic-C(C )=1 l42-143 acid 1 40-14 1 butyric C I'Ia-C HCH; (B) acidmethoxyacetic -CH OCH;; 115-117 anhydride m-methoxy- 143449 benzoic (B)acid isatoic 152-153 anhydride NHz dimethyl 147-143 tere- 000C11 Bphthalate diethyl CH,COOC H 100- 1 01 malonate diethyl -CH2COOC2H5 143-144 malonate (B) m-toluic 1 19-120 acid (B) 52 (CH2)amethyl N02 1512:

, m-nitro- 1-1 5 1 .5

benzoate EXAMPLE 5 3 100 parts of polyester cloth is dyed for 1 hour at125 C in a dye liquor containing 4,000 parts of water, 1 part 0 of thedye of Example 1 in a finely divided form and 3 EXAMPLE 54 100 parts ofpolyester cloth is dyed for 1 hour at 100 C in a dye liquor of 4,000parts of water which contains 1 part of the finely divided dye accordingto Example 2 and finely divided o-phenylphenol as a carrier. A brightpink dyeing is obtained having excellent light, wet and thermal fastnessproperties.

EXAMPLE 5 5 100 parts of cellulose acetate cloth is treated for 1 hourat C in a dye liquor of 4,000 parts of water which contains 4 parts ofCastile coap and 08 part of the dye of Example 23 in finely dividedform. A bright pink dyeing is obtained having good fastness properties.

EXAMPLE 5 6 100 parts of cellulose triacetate skein is dyed for 1 hourat boiling temperature in a dye liquor of 2,000 parts of water, 2 partsof the reaction product of oleylamine and 10 moles of ethylene oxide and1 part of the finely divided dye of Example 1. A full brilliant pinkdyeing is obtained having good fastness properties.

EXAMPLE 5 7 100 parts of polyamide cloth is dyed for 1 hour at C in adye liquor of 3,000 parts of water, 0.6 part of the finely divided dyeof Example 19 and 2 parts of sulfonated sperm oil alcohol. A bright pinkdyeing is obtained having good fastness properties.

I claim:

1. A red anthraquinone dye of the formula wherein X is hexamethylene andR is a member selected from the group consisting of hydrogen, aliphatichydrocarbon of one to five carbon atoms which is unsubstituted or whichcontains one halogen atom or one cyano, keto, carboxylic ester or phenylgroup as a substituent, and phenyl which is unsubmethoxy, nitro, aminoor carboxylic methyl or ethyl ester.

3. The dye having the formula:

Po-ww UNITED STATES PATENT @FFECE 569 CERTIFICATE QFCORREC'HQN Patent 3687 95 5 Da ted "Augu st 29 1972 Inventor (s) Karl M'air It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 1, line 5 CH CL ld 198d 9H CL I CL S 1gned and sealed this 20t hday of Marchl973,

(SEAL) Attest:

EDWARD M.FLETCHER,JR. [ROBERT GOTTSCHALK Atte'sting Officer Commissioner0f Patents I

2. A dye as claimed in claim 1 wherein R is phenyl or phenyl substitutedby halogen, hydroxyl, methyl, methoxy, nitro, amino or carboxylic methylor ethyl ester.
 3. The dye having the formula: